Distillation process



April 12, 1938 P. J. RoELFsEMA 2,113,965

DISTILLAT'ION PRocEs Filed July 6, 1957 2 Sheets-Sheet 1` April 12, 1-938- P. J. RoELFsx-:MA 2,113,965

DISTILLATION PROCESS Filed July 6, 1937 2 Sheets-Sheet 2- Patented Apr. l2, 1938' p PATENT OFFICE nrs'rnLA'rroN rnooEss Petrus Jurjen Roelfsema, Long Beach, Calif., as-

signor to Shell Development Company,

San

Francisco, Calif., a corporation of Delaware Application July s, 1931, serial No. 152,045

25 Claims.

'/ into tlir componentgroups. The present ap'- each consisting of a large number of individual'` plication is a continuation-impart of my `ap plication Serial No. 48,861, led November 8, 1935. e It has already been proposed to employ separating agents to aid in the separation of certain mixtures whichcannot be separated by normal fractionating method, for the reasons that they containsubstanc'es which have the same oralmost the same vapor pressures, or which form azeotropic mixtures. For example, Brame and Hunteri, in the Journal of the Institution oi?l Petroleum Technologists, vol. 13, (1927) page '794, et seq., propose the separation of a mixture of cyclohexane and benzene by distilling lit in the presence of ethylene-chlorhydrin, whereby the cyclohexane is caused to distill oi and the benzene isconcentrated in the residue.

However, many of industrial materials, which it is often desirable to separate into groups of components, are complex mixtures of chemically different groups of substances, some or all groups being mixtures of many various individual compounds of the same type, having wide boiling temperature ranges. While it is impossible in such cases to effect the separation into several narrow groups of similar compounds by any single treatment, it is an object of the present invention to provide a convenient method for dlrectlyseparatingsuchrelatively wide boiling range mixturesintoseverai groups of.similar compounds without iirst distilling the mixture into relatively narrow fractions of the range required for subjecting the 'fraction to a single distilling operation of the type described by Brame and Hunter.

Briefly, when used to separate, for instance, a mixtureof two groups of substances A and B,

compounds and each boiling throughout approximately the same boiling range, into, say, four portions: low-boiling A, high-boiling A, lowboiling B, and high-boiling B, the process of my invention consists of:

'(1) Distillingpthe mixture in the presence of a separating agent, such as a preferential solvent for one group `of substances, say, B, said agent being selected so that its vapor pressure and solvent characteristics would cause it to distill together with all of or with only the lower-boiling members of the group A, leaving all or a part of the members 'of the group B of boiling points corresponding to the distilled member of the group A undistilled. The undistilled portion may also include higher-boiling components of both loo groups, together with the high-boiling components of the mixture. By a preferential solvent vfor B is meant a solvent possessing such characsolvent and the mixture being treated is greater for B than for A when a mixture of all three components is brought to a temperature which is low enough to cause the system to separate into two liquid phases. However, other substances which do not form two layers when commingled with the mixture,l but which have a preferential solvent amnity for B, and therefore act to cause the component A to be distilled over at lower temperatures than the component B when distilled with the mixture beingl treated, may also be employed. The designation separating agent of the type of preferential solvents is in the present specification and claims used to include both of these ltypes oi' separating agents. While any preferential'solvent for B would cause, when distilled from a mixture of equally volatile A and B, the distillation of A in. `preference to B, the boiling temperature of the solvent plus A being lower than the. initial boiling temperature of the solvent-free mixture, it is preferable, in order to obtain relatively easily a substantial yield of A in the distillate, to use a solvent which boilsjj"` A to be distilled from the mixture.

(2) Either or both distillation products from the foregoing step are distilled in the absence of selective solvent to produce'seco'nd distillation products. For example, the rst distillation within or near the boiling range of components residue, consisting of low-boiling Bs and highboiling components of the mixture, `may then be distilled in the absence of av selective solvent to distill oil low-boiling component B, which may Ahave a boiling range corresponding to that of the already separated low-boiling As. Alternatively, or in addition, the iirst distillate from the iirst distillation is freed from the separating agent by any suitable means, such as extraction, or chilling and causing the-formation of liquid phases which may be decanted, and the solvent-free portion is distilled to produce a distillation residue whichk contains a concentrate of the highest boiling members of component A contained in said first second distillate.. For example, the residue produced by the second distillation of the rst d istillation residue, consisting of the high-boiling As and Bs, may then be distilled in a manner similar to the rst distillation, in the presence of the same of of another separating agent to produce a third overhead product containing substantiall only high-boiling As together with the separati g agent and a third bottom product. If the second bottom product has 'a suillciently narrow boiling range, this third distillation can be conducted so as to produce a third bottom product substantially free of the members of group A, and at the same time a distillate substantially free from members of the group B. If not, the third bottom product may contain both rA and B, and may be further distilled in successive distillations. Thus,vthis invention provides a method whereby a sharp separation of at least two groups of substances boiling within coinciding boiling ranges can be eiected, or their concentrates, can be produced, by two alternating series of.distillations: one series of distillations carried out Ain the presence of a separating agent and another series without such a solvent.

The nature of the invention may be more fully understood iromthe drawings, which will be described with reference to a process for separating a mixture of paraflinic hydrocarbons (group A) and aromatic .hydrocarbons (group B) in a continuousprocess, although my invention may be applied to the treatment of many other types of mixtures and may be practiced in batch or discontinuous operations as well.

Thus, hydrocarbon mixtures, such as gasoline, kerosene, Diesel fuel, and other distillates, may contain several or all of the following types of hydroycerggnsfor which separating agents of the t of preferential solvents have different degrees of ailinity; straight-chain and branchedchain es and olenes, alkylated and unalkylated naphthenes and aroma-tics, both monoand poly-cyclic, and partially hydrogenated aromatics. In addition to these hydrocarbons, many distillates contain non-hydrocarbon compounds, such as sulfur-containing compounds. VOne or more of these types of compounds for which the separating agent has the lowest amnity lmay be regarded as the group A, while one or more of the types for which the separating agent has the I greatest amnity may -be regarded as the group B,

'the inventionj and Fl all of theconstituents of the initial mixture being thereby classiiled in one of these groups when operating to produce but two types of products. When operating to produce more than two types of products, the initial mixture is separated into more than two groups of' substances, all of which may be hydrocarbons, although in certain cases, one or more of these groups may consist mainly of non-hydrocarbons, as explained more fully heref inatter in connection with Figures 2 and 3.

In the drawings, Figure 1 is a schematic flow diagram of one embodiment of my process for separating a mixture into two groups of consecutive fractions; Figures 2 and 3 are similar diagrams, partly in section, of two specific forms of portions of apparatus show'n in Figure 1, suitable for carrying out m d embodiments of 4 is a schematic ow diagram of a second embodiment of my process.

Referring particularly to Figure 1, a hydrocarbon mixture to be separated, such as a kerosene distillate, and a separating agent, such as aniline. are fed from sources I and 2 through valves 3 and I, respectively, into a mixer 5 and a fractionating ,column i, provided with a reboiler 1, and Awith the necessary contact means, such as lmbble-platesor packing, for eecting fractional distillation. The reilux in the column may be produced and controlled by means of a partial condenser 8, located Anear the top oi the column, or by' a separate condenser 9 connected with the top of the ,column Abyva vapor conduit Ia, a reux line I0, provided with a manually or thermostatically operated valve I I. The top product may be taken oi through a conduit I2 -.and valve I3. and introduced into a separating apparatus I4, where the aniline is separated from the low boiling parafllnic hydrocarbons, and returned to the tank 2 through a conduit I5, the hydrocarbons being withdrawn at I6.

The apparatus Il may consist of a chilling device and a settling tank, wherein the aniline and paraiiinic drocarbons are allowed to stratify. If the hydrocarbon layer contains appreciable quantities of the separating agent as when the temperature is not low enough to ,insure substantially complete separation, or when a less immiscible separating agent is employed, Ithe product withdrawn .at I6 may be further fractionated by washing, freezing, or distillation to separate the last traces o1 the agent from the* Alternatively, the apparatus hydrocarbons. may be an extraction unit, wherein the mixture is washed with water or with a similar liquid,

'I'he degree to which this is accomplished de-- pends upon the degree of rectication which is eiected by the column, and it is understood that lmy invention is not restricted to processes which produce an overhead product which is completely free from members of group B. Moreover, in certain mixtures the overhead mixture in the column 6 may be a ternary or higher azeotrope containing certain amounts oi substances of .group B. I prefer to' select the separating agent so as to produce an overhead mixture which is free from azeotropes containing members of group B, or which contain azeotropes which contain the components of B in minor proportions; Abutmy invention is not restricted to such a choice oi separating agents, inasmuch as it is possible to eiIect a complete separation of these complex overhead mixtures by operating in accordance with the process described and claimed in my copending application, Serial'No. 12,007, illed March 30, 1935.

'I'he bottom product from the column 8, which contains substantially all of the aromatics (i. e., the members of group; B) and the higher boiling parailins (i. e., the gher boiling members of group A) is withdra at I'I, the rate of withdrawal being regulated by a valve I8, which lmay be automatically controlled. .The process, as'

.preceding stage, such as that from the outlet I1,

is introduced into a fractionating column I9 through a valve 2l and a conduit 2|. The column Il maybe similar to the column I, in that it is 7` shown, as well as with the usual bubble plates or packing. In composition in the conduit 2l should be substantially or completely free from aniline 'or from any other separating agent which is introduced from the tank 2. In the absence of the separating agent, the aromatics or a concentrate thereof, which normally boil below the paraiiins which. are present in the feed mixture in the conduit 2| can be distilled off in the column I9, as an overhead product, and withdrawn at 24, while the heavier paraiiins and aromatics are withdrawn at 25, as a bottom product, and introduced into a surge tank 26. The column I9 is preferably operated so that substantially no parafilns are removed with the overhead product, although the degree to which` this condition is achieved may vary depending upon the eiliciency of the column. The nature of the column and the resulting degree of rectification which will be obtained in any situation will be dictated by economic considerationsyand it is pointed out that my invention is vnot restricted to a process in which only a comeected.

The hydrocarbon mixture from the tank 26 and a separating agent from the tank 21 are introduced into a mixer 2l through valves 29 and 30, and the resulting mixture is distilled in a fractionating column 2|, which may be similar to the column 0. and provided with suitable contact means, not shown, a reboiier 22, and a partial condenser 33, or with an external reiiux condenser of the type shown in connection with the column 8. The separating. agent in the tank 21 may be the same as that which was employed in the first stage, or may be another agent which may boil either'above or below said first agent.

I have found that if an agent having a high vaporpressure is chosen as theseparating agent, rectiilcation in the columns 6 and 3| is easier,

'but the overhead mixture will generally contain quantities of this liquid, often it is much more diiilcult to fractionate such a mixture, thereby often necessitating the use of a. higher fractionating column and/or a higher reflux ratio. I have lfound that the best results are often obtained y`by employing inyeach stage of theprocess a separating agent which has a boiling point which is near the initial boiling point of the mixture being fractionated. Thus, I prefer to employ as 7 4a separating agent, a liquid selective solvent boiling within the range of temperatures: 25 below the initial boiling point of the mixture to the end point of the fraction distilled in the overl head, although I prefer to employ a separating agent with a boiling point not more than 10 yIf the hydrocarbon mixture in the tank 26 has a sufliciently narrow boiling range, saynot in excess of about 40 to 60 C.,A the column 3| may be operated to remove continuously all of the parafiinic hydrocarbons, or all those' paraiiinic hydrocarbons which it is desired to remove from the bottom product by the operation of the process in the overhead product, which is withdrawn at 34, and to withdrawsubstantially all of the high-boiling aromatic` hydrocarbons in the botlated by, a valve 36. The top product may be further treated in the apparatus 31, which may in the' column I9 in the absence of the separat- N ing agent, or with substantially reduced amounts of a separating agent,and the second redistillation in the column 3| with an additional' quantity of -a separating agent constitute the second stage \of my process. Any number of stages, similar to the described second stage may be employed,

' depending upon: the width of the boiling range of the initial mixture in the tank I, the solvent characteristics of the components of the mixture and thef polar separating agent, the volatility of the separating agent selected, and the width of the fractions separated at each stage. For example, if the mixture in the tank 26 has too wide a boiling range to permit the effective separanection with column 6, to produce a top product containing only a, portion of the parains contained in the said mixture, thereby producing a bottom product at`35 which: contains both paraiiins. and aromatics. This bottom product can then be fractionated in one or more additional stages, each similar to the secondstage, until the desired'separation between paraiiins and aromatics has been effected. Or, if desired,

the column 3| may be operated in the manner described for column |06 of Figure 4.

As was pointed out above, the material which is fractionated in the first column of each stage after the ilrst stage should contain little or no separating agent. 'Ihis condition may be established in various ways. According to my preferred mode of operation, I operate the column 6, so that the bottom product withdrawn at I'I will be substantially free of the separating agent. This mode'of operation, subsequently described, may be applied to the succeeding columns or distillation steps in which a mixture is fractionated in the presence of a polar separating agent, although it is not necessary that the bottom prod` uct from the last of these operations be free of the `separating agent.

To produce a bottom product at I1 which is free from theseparating agent, and at the same time remove the desired fraction of parafiins in the top product introduced into the apparatus I4, the ratio o i the separating agent to those parailins which are in the said top product must be the same as in the feed introduced into the column 6. This may be eiected by controlling the valves 3 and 4 to introduce these materials into the mixer 5 and column 6 in thel ratio in which they occur in the natural overhead product, i. e. the vapors passing through the vapor conduit I 0a.; the overhead product will often but ratio as these substances occur in the feed mix.

:bottom product.

need not be an azeotrope or a pseudo-azeotrope of more or less xed composition.

Alternatively, the top product may be produced by closing the valve I3, opening valve '40 and passing a portion of the overhead mixture through a chiller 4I, and permitting the chilled mixture to separate into two liquid phases in a phase separator 42. A portion of one of these phases, or, if desired, a mixture lof both phases, is returned to the column 6 through a conduit 43, either together with the reflux condensate at I0, or separately at any desired point in the column, as shown, the quantity and composition being controlled by the valves 44 and 45, so that' the portion withdrawn from the separator 42 through valves 46 and 41 contains the separating agent and the distilled parafilnic fraction in the same ture. It should be noted that the stated relationship concerns only those parailins which are removed in the overhead mixture, and not the total paramn content of the feed mixture. AThe free of the separating agent, and may be withdrawn as a product of the process, thereby eliminating the apparatus I4. If it contains substantial 4quantities of this agent it may be further fractionated or otherwise treated in the apparatus I4. 'I'he phase withdrawn at 41 willoften consist substantially only of the separating agent and may be returned directly to the tank 2, as shown, or may be further treated, as desired. If the density of .the separating agent is less that of the desired overhead product, the polar liquid will be recovered as the upper phase at 48, instead of at 41.

It should be noted that the desired composition relationship may be established by analyzing the feed 'mixture and the top product; butin practice, this will often be empirically determined by manipulating the valves 3 and 4, and/or the yalves 44, 45, 46, and 41, so as to produce the desired Moreover, the composition of the bottom product can be controlled byregulatim the above valves to maintain a co'nstant temperature at a selected point ofthe column, or in accordance with the method described i the patent to Kramer, No. 2,022,809. These methods of controlling the composition are more fully described in my copending application, Serial No.

l12,001, to which reference may be had for further bottom product at I1 may be produced free from Athe separating agent by regulating the temperatures and/or the pressures in the column 6 so as to distill over all of the separating agent. 'Ihe method necessitates only an approximate adjustment4 of the valves 3 and 4 in accordance with the rule given above, and may often cause the overhead product to contain'appreciable quantities of aromatics. In processes in which complete separation is not essential this mode of operation may, however, be permissible.

According to still another modeof operation the bottom product at I 1 may contain appreciable quantities of the polar separating agent, which may be removed therefrom by passing the bottom product through an apparatus 4l, by closing the valve 2l and opening the valve 4l. The apparatus 48 may be similar to the apparatus I4,

described above, and designed to remove the' While I have described the' invention with reference to a continuous process, employing a separate piece of apparatus for each successive operation, the invention may be practiced in a single distillation column,as will be apparent from the following example:

Six parts by volume of a 240 C. fraction of a kerosene distillate having a refractive index n of 1.462 were mixed with ve parts by volume of o-cresol (B. P. 181 C.), charged into a still, and distilled at atmospheric pressure. After the first three fractions consisting of the cresol and low-boiling, low-refractive index hydrocarbons were distilled (fractions lin the following table) the still residue was substantially free from o-cresol. This still residue was further distilled to yield a low boiling hydrocarbon fraction of high refractive index (fraction 4). 'Ihis distillation was continued until all of the low boiling hydrocarbons of high refractive index were recovered in the overhead, as indicated by the refractive index of the overhead vapors. To regulate this distillation the refractive indices of successive portions of the overheadv were determined. and the distillation was stopped as soon as the refractive index of the overhead product began to decrease. In this distillation'the maximum refractive index of 1.477 was reached when the still temperature reached approximately 212 C.,

' removed from the residue. 'I'heresidue was further fractionated into fractions 8 and 9.

Percent of Still-head Rmctive Hydrocarbon fraction ori temperature index of f dis liste range C. fraction ng Dinamica-Uitl verno! Dbllalml without alma muum 1a warmem Didillalon without solvent Comparing this process with that described heretofore with reference to Figure l of the drawings, it should be noted that the fractions 1 to 3 correspond to` the product withdrawn at I6 (or through thevalve 49); fraction 4 to that withdrawn at 24; fractions 5 to 7 to that withdrawn at 39,; and fractions 8 and 9 to that withdrawn at 35. Although these four products have, in this example, been fractionated into narrower cuts, it is app rent that this was done merely tov show the exaft course of the process, and that .this would ot always be a necessary part of my' process. It should also be noted that the fractions Ltirii contain the low-refractive index hydrocarbons which have normal boiling temperatures between 195 and 220 C., while fractions 5 to rl contain low-refractive index hydrocarbons which have normal boiling temperatures between 220 and 240 C., so that, by combining fractions 1-3 and 5-7, a full-range aromatic-freekerosene can be obtained, while fractions 4, 8, and 9 represent aromaticconeentrates, which may be used. for instance, as aromatic diluents in solvent extractions of lubricating oils.

My process may also be applied to operations in which more than two types of products are produced, by providing the fractional distillation columnwith side strippers. Columns of 'this type may be employed in Iany or all stages of my process in place of the columns described above.

One form of this type of column is shown in Figure 2, where 6' represents a fractionating column, which may be similar to the column 6 of Figure 1, and-may be provided'with heating and condensingand/orrefiux means, and provided with the usual bubble plates 50, a's shown.

or with any other means for effecting contact between the rising vapors and descending reflux condensate. The feed mixture is introduced through the mixer 5, and the top and bottom products are withdrawn -at the opposite ends of the column, as described heretofore. At an/intermediate point of the column, as, for example, at 5 I, a portion of the distillation mixture is withdrawn and further distilled in a side stripper 52, which may be equipped with a re-boiler, and a reflux condenser, to produce two products of different boiling ranges, one of which isfwithdrawn as a product, as at 53, and the other is returned to the column 6' through the conduit 5I, at any convenient`point, preferably to a plate at which the composition is most nearly likethat of the returned product. While I may withdraw either the vapors or the condensate from the column at 5|', and may take off either the top product or the bottom product from the side stripper, depending upon the nature of the side productdesired, I prefer, when removing a side stream from a point above the feed intake, to remove a condensate, and to return to the column the lower boiling portion from the side stripper.

One or more of such side streams may be removed from the column 8. When removing a side stream from a point below the feed intake,

f as, for example; at 5,5, I prefer to remove the vapors, and to return to the column the bottom product from the Sidef'stripper 56, as through a conduit l5l, and withdraw as theV intermediate product the top product, produced at 58, although this choice of mixtures is not vital.

` If desired, additional'quantities of the same or a different separating lagent may be introduced through the'conduits 59 or 60, thereby improving the fractionation in the side strippers 52 and 55.

I may also operate the side strippers in the absence of the selective solvent, as shown inl Figure 3, in lwhich l' is a fractionating column, similar to that of Figure 2. The side streamwithdrawn from the column B' at 6| is passed through a separating unit 62, in which the separating agent is removed from the side stream. This unit 62' may be similar to the separators il and 48, in which the 'separating agent is removed by chilling and stratification, or by washing with a suitable sol-y vent, etc., whereby a side streamentirely or substantially free from the separating agent is produced. 'I'his product is introduced through a conduit Il into a side stripper 64, where it is distilled to produce two products, one of which is withdrawn at 85 as a side product, and the other is returned to thecoiumn 6' through a conduit 86 and a manifold '81, the returned product being preferably returned to apoint at which the composition of the distillationl mixture is similar to that of the returned portion. While either vapors or condensate may be withdrawn at 6|,.-and either the top or bottom product withdrawn from. the side stripper, I prefer, when separating aside stream from a point in the column 6 above the feed intake, to separate a condensate, and to withdraw the top product of the side stripper as a side product, and to return the bottom product to the column 8'. f

One or more of such side streams may be withdrawn from the column 6. When removing a side stream from a point below the feed intake, as, for example, at 68, I prefer to remove vapors, which may be freed from the separating agent in *the apparatus E9e-as described above for the ap- 4 paratus (52,-and distilled in the side stripper 10. In this case, I prefer to withdraw` the bottom product from the side stripper 10 as a side product at 1| and to return the more volatile portion through a conduit 13 and manifold 14. My process is not, however,'limited to the choice of products indicated above for the preferred mode of operation. The above described embodiment may be employed to produce several hydrocarbon products.v Often, when fractionating a mixture, like gasoline or kerosene, which may be regarded as consisting of three groups'of components of progressively greater solubilities in selective solvents, the order being. for instance, paramnic hydrocarbons, non-parafdnic hydrocarbons, and sulfurbearing substances, particularly of thiophene series, the fractionation in me column 6' may be so adjusted, by providing a suflicient reflux, the necessary amount of solvent, and a column of proper height, that the most soluble (sulfur) components are concentrated at the bottom product, substantially all components solubilities (non-paraines) are removed as a .side stream product (through either conduit 59, or 58, or 65, or 1|), and the low-boiling members of the least soluble group of substances are produced at the top of the lcolumn 6'. In this case, l this side stream iproduct is often used as the feed to the column I9 and not the bottom product of column B. v

In the form of the invention illustrated in Figoi intermediate ure 4, the distillate produced by 'thefdistillation in the presence of separating agent is further distilled. In this figure, the mixture to be separated and theV separating agent are fed `from sources Ilii and I 02 through valves Hilfy and |04, respectively, into a mixer |05 and a fractionating column |06, provided with reboiler |01, partial condenser |08, condenser |09, vapor conduit I|0a, reux line ||0` and redux valve lil, top

product line ||2 and valve lllseparating apparatus ||4, solvent return line ||6, and bottom product draw oil line ||1 and valve ||8,' all similar to the apparatus heretofore described in conin place of, or in addition to the separator ill. vIn this embodiment of the invention the temperature and/orpressure are regulated so that the irst top product, flowing through the conduit ||2 contains an appreciable quantity of members l of the group B. Due to the effect of the` separating agent, thisv irst top product will contain members of group A boiling below the members of group B contained therein.

In the second stage of my process the rst top product, after the removal of all or substantially all of the separating agent, is introduced through a valve |20 and a conduit v| 2| into a fractionatg ing column I9, which may be similar to the' column I06,and equipped with va heating coil |22 and a partial condenser |23. In the absence of the separating agent the members of group A,

such as parailns, or a concentrate thereof, which normally boil above the members of group B, such as aromatics, which are present in the rst top product fed through the conduit |2| are obtained in the seconddistillation residue, and withdrawn at |25, while the lighter members of both groups (or only of group B, when no lighter A members of group A are present) are withdrawn at |24 as a second top product. and vmay be withdrawn as a product, or introduced into a surge tank |26. The column I9 is preferably operated so that substantially no members of the component B are present in the bottom product, although the degree to which condition isl achieved may vary depending upon the eiiiciency of the column, and upon the purity of the product desired, my invention not being restricted to the formation of a bottom product from the column ||9 which contains only A. y

The second top product in the tank |26, together with a separating agent from the tank |21, (which may be the same as that'in the tank |02, but is preferably of a lower boiling point, the relation f its boiling point to the boiling range of the mixture being desirably that dis-y closed above in connection withfthe separating agent from the source 21 in Figure 1) are introduced into a mixer |26 through valves |20 and |30, and the resulting mixture is distilled in a fractionating column |3| which may be similar to the column 6 of Figure 1, and provided with suitable contact means, not shown, a -reboiler |32, and a partial condenser |33, or with an external reilux condenser of the type shown with column 6 in Figure 1. If the mixture in the tank |26 has a sufliciently narrow boilingrange, say not in'excess of 40 to 60 C., the column |3| may be operated to remove continuously all of the members of group B, such as the aromatic hydrocarbons, or all of those which it is desired to remove from the ultimate top product in the third bottom product, which is withdrawn at |35, the rate of eiliux being regulated by'a valve |36,

and to withdraw substantially all of the members-v of group A, such as parailnic hydrocarbons, in

the third overhead vproduct at |35. The top product may be further treated in theapparatus |31, vwhich may be similar to the apparatus Il,

described in connection with Figure 1, from whichthe separating agent is returned to storage via the line |36 and the low boiling members of group A are withdrawn at |36.

If either or both of the distillation products from the column |3| contain members oi' both components, such product may be further separated by any desired additional number of stages. Thus, if the third top product contains both A and B, it may, after the removal of the separating agent, be further distilled in one or more stages comprising a column similar to the column ||9 and 'column similar to the `column |3|. The third bottom product, ii' it contains both A and B. may be treated in one or more stages similar to the lsecond stage described in connection with Figure 1,'comprislng the distillations in the column I9 alone, or both columns I9 and 3|.

The bottom product withdrawn at ||1 from the column |06 may contain substantially only members of the component B, either with or without separating agent. If, however, it contains both A and B, it vmay be treated in the manner described above for the bottom from the column 6 in Figure 1.

The embodiment 'oi' the invention illustrated in Figure 4 may be employed to treat any type of mixture, such as mixtures of hydrocarbons, or oils containing one type or several types oi' hydrocarbons together with sulfur compounds. In the latter case, the column |06 may be operated so as to remove a concentrate of sulfur compounds at as the bottom product, removing the greater portion of the hydrocarbons in the rst top product. After the removal oi' the solvent the latter maybe redistilled inthe column ||9. or treated either in the column |3I,

or in the column 6 of Figure `1 as an initial mix' ture -mixture of polar substances, or a mixture oi' a' 'polar substance and a non-polar substance, a

hydrocarbon may often be employed as the selective solvent. This invention is, therefore, to be construed broadly to include alll forms of "extractive distillation,.as describedin-the rst part of this speciiication. For example, mixtures oi fatty oils may be separated from impurities of about the same boiling temperature range by the process of the present invention. Suitable separating agents for effecting .the separation of hydrocarbon mixtures will-be apparent to those skilled in the art. Among the separating agents which are often not true preferential solvents, in that they are not capable oi' causing the formation of two layers when mixed with the lighter distillates, but which are included in the desigthe term component Ais not restricted to pure product present speciiication and claims.'

-products of the process, depending upon their volatilities and their susceptibility to the separating agent employed.

I claim as my invention: I

1. A process for separating a mixture containing a rst and asecond component, each of said components containing a 'plurality of substances having different boiling temperatures, and the first component containing substances boiling within the boiling temperature range of the second component, comprising the steps of distilling said mixture in the presence of a separating agent of the type of preferential solvent for members of the second component under conditions to produce a first top product containing the separating agent together with at least the lowest boiling members of the 'rst component, and a first bottom product, and distilling one of said first distillation products substantially in the absence of the separating agent to produce second top and bottom products containing relatively -lower and higher boiling substances of the mixture. i

2. A process for separating a mixture containing a rst and a second component, each of said components containing a plurality of substances having different boiling temperatures, and the rst component containing substances boiling within the boiling temperature range of the second component, comprising the steps of distilling said mixture in the presence of a separating agent of the type of a preferential solvent for members of the second component under conditions to produce a ilrst top product containing the separating agent together witha concentrate of the lowest boiling members of the first component boiling within the lboiling temperature range of the second component, and a iirst bottom product, and distilling the first bottom product substantially in the absence of the separating agent to produce a second topproduct containing a concentrate of the ylowest boiling members of the second component contained in said rst bottom product and a second bottomproduct containing higher boiling substances of the mixture.

3. A process for separating a mixture-containingla rst and a second component, each of said components containing a plurality of substances having different boiling temperatures, and the first component containing substances boiling within the boiling temperature range of `the second component, comprising the steps of distilling said mixture in the presence of a separating agent of the type of a preferentialsolvent for members of the second component under condi- 'tions to produce a 'iirst top product containing the separating agent together with at least lowboiling members of both components and a first bottom product containing a concentrate of the highest boiling members of the second component boiling within the boiling temperature range vof ne nrst component, removing the separating agent from the first top product, and distilling the said first top product substantially in the absence of the separating agent to produce a second bottom product containing a concentrate of the highest boiling members` of the rst component contained in said rst top product, and a second bottom product containing relatively lower boiling substances of the mixture.

4. A process for separating a mixture containlng a first and a second component, each of said -components containing a pluralityof substances having different boiling temperatures, and the first component containing substances boiling within the boiling temperature range of the second component, comprising the steps of distilling said mixture in the presence of a separating agent of the type of a preferential solvent for members of the second component under conditions to produce a rst top product containing at least the lowest boilingv members of the first component and a first bottom product, distilling' one of said first distillation products substantially in the absence of the separating agent to produce second top and bottom products containing relatively lower and higher boiling substances of the mixture, and distilling one of said second distillation products in the presence of a separating agent of the type of a preferential solventfor members of oneof said components under conditions tov produce third top and bottom products,

said third bottom product containing members ond'component, comprising the steps of distilling said mixture in the presence of a separating agent of the type of a preferential solvent for members of the second component under conditions to produce a first top product containing a concentrate of the lowest boiling members of the first component boiling within the boiling temperature range of the second component, and a first bottom product, distilling the first bottom product substantially in the absence of the separating agent to produce a second top product containing a concentrate of the lowest boiling members of the second component contained in said first bottom product and a second bottom product containing higher boiling members of both components and distilling the second bottom product in the presence of a separating agent of the type of a preferential solvent for members of one of said components under conditions to produce a third top product containing a concentrate of members of one of said components,n

distilling said mixture in the presence of a separating agent of thetype of a preferential solf vent for members of the second component under conditionsto produce rst top and bottom distillation products, at least one .of which contains members of both components, redistilling the first distillation product containing members of both components substantially in the absence of the separating agent to produce second top and bottom distillation products, the

-second distillation product corresponding to the members of one of said components under conditions to produce third top and bottom products, said third bottom product containing members of the preferentially dissolved component boiling Within the boiling temperature range of members of the other component contained in said third top product. 4

7. A process for separating a mixture contain-- ing a first and a second component, each ,of said components containing a plurality of substances covering a wide range of boiling temperatures,

and the rst component containing substances boiling within Athe boiling tempenature range of the second component, comprising the steps of distillingsaid mixture in the presence of av separating agent of the type of a preferential solvent for members of the second` component under conditions to produce a ilrst top product containing the separating agent and at least low boiling members of both components and a first bottom product containing a concentrate of the highest boiling members of the'second component boiling within the boiling temperature range of the iirst component, removingvthe separating agent from the first top product, distilling the said ilrst top product substantially in the absence of the separating agent to produce a second bottom product containing a concentrate of the highest boiling members of the rst component contained in said first top product and a second product containing lower boiling members of both components, and distilling said second product in a third distilling stage in the presence of a separating agent of the type of a preferential solvent for members of the second components under conditions to .produce third top and bottom products, said third bottom product containing members of the preferentially dissolved component boiling within the boiling temperature range of members ofthe other component contained in said third top product, and said third top product containing the separating agent employed in the third distilli'ng stage.

8. A process for separating a mixture containing a iirst and a second component, each of said components containing a plurality of substances' covering a wide range of boiling temperatures, and the rst component containing substances boiling within the boiling temperature range of the second component, comprising the steps of distilling said mixture in the presence of a separating agent of the type of a preferential solvent for members of the second component under conditions to produce a rst top product consisting of the separating agent and a concentrate of the lowest boiling members of the first component boiling within the boiling temperature range of the second component, and a iirst bottom product, distilling the first bottom product substantially in the absence of the separating agent to produce aliases a second top product containing a concentrate of the lowest boiling members of the second component contained in said flrst bottom product and a second bottom product containing higher boiling members of both components, and. distilling the second bottom product in the presence of a separating agent of the type of a preferential solvent for the members of the second component present in said second bottom product under confditions to produce a third top product consisting 10 of the separating agent and a concentrate of members of the iirst component, and' a third bot- 11. The process according to claim 9, in which 25.Y

the separating' agent employed in each distilla- Y tion has a'boiling temperature which is within the range: from lC. below the initial boiling point ot the fraction distilled in the respective 3o distilling operation to its end point.

12. A process for separating a mixture containing a rstand a second component, each of said components containing a plurality of substances havlng different vboiling temperatures,

land the first component containing substances boiling within the boiling temperature range of the second component, comprising apreliminary treatment which comprises distilling the mixture in the presence of a separating agent of the type of a preferential solvent for the members of the second component under conditions to produce a preliminary top product containing a concentrate of the lowest boiling members of the rst component boiling within the boiling temperature range of the second component, and a preliminary bottom product, followed by' at least onecycle of treatment, each cycle comprising the combination of steps of distilling the bottomv product of a preceding distillation treatment substantially in the absence of a separating agent to produce a rst top product containing a concentrate of the lowest boiling members of the second component which are present in the bottom product being distilled in the respective cycle, and a iirst bottom product, and distilling the rst bottom product in the presence of a separating agent of the type of a preferential solvent for the members of the second component under con- Vdtions to `produce a second top product containing a concentrate of members of the first component boiling within the boiling temperature range of the members of the second component contained in the said first bottom product, and a second bottom product, each of the said second top products except that produced in the last cycle of treatment containing a concentrate of only the lowest boiling members of the first component which are present in the bottom product being treated in the respective cycle.

l 13. The process according to claim 12 in which 70 the separating agent employed in each distillation has a boiling temperature which is within the range: from 25 C. below to 10 C. above the initial boiling point of the mixture being distilled in the respective distilling operation.

14. A process for separating a mixture containing a plurality of components, each of said components containing a plurality of substances having diierent boiling temperatures, and at least some of the members of each component boiling within the boiling temperature range of the other components, comprising the steps of distilling saidv mixture in a fractionating zone in the presence of a separating agent of the type of a preferential solvent for the members of a iirst of said components under conditions to produce a top product consisting of the separating agent and a concentrate of the lowest boiling members of one of said other components boiling within the boiling temperature range of another component and a bottom product, withdrawing `a portion of the distillation mixture from an intermediate point of said zone, distilling the withdrawn mixture into several side products, and returning one of said side products to the fractionating zone.

15. lIhe process according to claim 14, in which an additional quantity of a separating agent is added to the withdrawn mixture prior to distillation.

16;-A process for separating a mixture containing a plurality of components, each of said components containing a plurality of substances having different boiling temperatures, and at least some of the members, of each component boiling within the boiling temperature range of the other components, comprising the steps of distilling said mixture in a fractionating zone in the presence of a separating agent of the type of a preferential solvent for the members o a iirst of said components, under conditions to produce a top product consisting of the separating agent and a concentrate of the lowest boiling members oi one of said other components boiling within the boiling temperature range of another component, and a bottom product, withdrawing a portion of the distillation mixture fr`om an intermediate point in said Zone as a side stream, removing the separating agent from the side` stream, distilling the residual portion of the side stream into a number of side products, and returning one of said side products to the fractionating zone.

17. A process for separating 'a hydrocarbon mixture containing at least a rst and a second hydrocarbon component, each of said hydrocarbon components containing a plurality of hydro.

carbons having diierent boiling temperatures,

and the rst hydrocarbon component containing uct substantially in the absence of the preferential solvent to produce a second top product containing a concentrate of the lowest boiling Amembers of the second hydrocarbon component contained in said rst bottom product, and a second ttom product, and distilling the second bottom roduct in the presence of a preferential solvent fer the members of the second hydrocarbn component under conditons to produce a third top product containing a concentrate of members of the rst hydrocarbon component. and

a third bottom product.

18. A process for separating a hydrocarbon Y mixture containing at least a first and a second hydrocarbon component, each o'f .said hydrocarbon components containing a plurality of hydrocarbons having different boiling temperatures, and the first hydrocarbon component containing hydrocarbons boiling within the boiling temperature range of the second hydrocarbon component, comprising the steps of distilling said mixture in the presence of a separating agent of the'type of a preferential solvent for the members of the second hydrocarbon component under conditions to produce a first topproduct consisting of the separating agent and a concentrate of the lowest boiling membersv of the rst hydrocarbon component boiling Within the boiling temperature range of the second hydrocarbon component, and a first bottom' product, and distilling the ilrst bottom product substantially in the absencerof the separating agent to produce a second top product containing a concentrate of the lowest boiling members of the second hydrocarbon component contained in said iirst bottom product, and a second bottom product.

19. A process for separating a sulfur-containing hydrocarbon mixture containing at .least a iirst and a second hydrocarbon component and a sulfur component, each of said hydrocarbon components containing a plurality of hydrocarbons having diierent boiling temperatures; and the first hydrocarbon component containing hydrocarbons boiling within the boiling temperature range of the second hydrocarbon component, comprising the steps of distilling said mixture in a fractionating zone in the presence'of a separating agent of the type of a preferential solvent having greatest solvent attraction for the sulfur component and an intermediate solvent attraction for the second hydrocarbon component under conditions to produce a first top product containing the separating agent and hydrocarbons of substantially reduced sulfur content and a rst bottom product containing a concentrate of the sulfur component, removing the separating agent from the rst top product, and distilling said irst -top product substantially in the absence of the` separating agent to produce second top and bottom products, the latter containing a concentrate of the highest boiling hydrocarbons of the first hydrocarbon component contained in said first top product.

20. A process for separating a sulfur-containing hydrocarbon mixture containing at least a rst and a second hydrocarbon component and a sulfur component, each of said hydrocarbon components containing a. plurality of hydrocarbons having different boiling temperatures, and the rst hydrocarbon component containing hydrocarbons boiling Within the boiling temperature range of the second hydrocarbon component, comprising the steps of distilling said mixture in a fractionating zone in the presence of a separating agent of the type of'a. preferential solvent having greatest solvent attraction for the sulfur component, and an intermediate solvent attraction lfor the second hydrocarbon component under conditions to produce a first top product containing a concentrate of the lowest boiling members ofthe rst hydrocarbon component boiling within the boiling temperature range of the second hydrocarbon component, and a rst bottom product containing va concentrate of the sulfur compounds, withdrawing a portion of the distillation mixture from an intermediate point in the fractionation zone as a side stream, distilling the withdrawn side stream into at least two intermediate products, returning one of said intermediate products to the distillation zone, distilling the other of said intermediate products substantially in the absence of the separating agent to produce a second top product containing a concentrate o! the lowest boiling members of the second hydrocarbon component, and a second bottom product.

21. A process for separating a sulfur-containing hydrocarbon mixture containlng'at least a first and a second hydrocarbon component and a sulfur component, each of said hydrocarbon components containing a plurality of hydrocarbons havingdiiferent boiling temperatures, and the first hydrocarbon component containing hydrocarbonsboiling within the boiling temperature range of the second hydrocarbon component, comprising the steps oi' distilling said mixture in a fractionating zone in the presence of a separating agent of the type of a preferentialsolven't having greatest solvent attraction for the sulfur components, and an intermediate solvent attraction for the second hydrocarbon component under conditions to produce a rst top product consisting of the separating agent and a concentrate of the lowest boiling members of the iirst hydrocarbon component boiling within the boiling temperature range of the second hydrocarbon component, and a iirst bottom product containing a concentrate of the sulfur compounds, withdrawing a po'rtion of the distillation mixture from an intermediate point in the fractionation zone as a side stream, distilling the withdrawn side stream substantially in the absence of the separating agent to produce a second top product containing a concentrate of the lowest boiling members of the second hydrocarbon component, and a second bottom product.

22. A process for yseparating a mixture containing a rst and a second component, each of said components containing a plurality of substances having different boiling temperatures. and the rst component containing substances boiling within the boiling temperature range of the second component, comprising topping said mixture in a series of distilling operations, the rst distilling operation and alternate distilling operations thereafter being carried out in the presence of a separating agent of the type of preferential solvent for the members of the second component, and other distilling operations being carried out substantially in the absence. of a separating agent.

23. In a process for separating a mixture of several components boiling throughout substantially the same boiling range and having different solubilities with regard to a preferential solvent for some of the components, the steps of distilling said mixture in a distillation zone in the presence.

of a separating agent of the type 'of the preferential solvent under conditions ..0 produce a top product consisting of the agent and a concentrate of the lowest members of the component least soluble in the solvent and a bottom product consisting essentially of the concentrate of the components most soluble in the solvent, withdrawing from an intermediate point of the distillation zone a side stream having the concentration of said most soluble components substantially below that of the original mixture and substantially free of the said lowest members of the least soluble component, removing the separating agent from the withdrawn side stream, sub- Jecting the residual portion of the side stream to fractional distillation in the absence of the separating agent to produce a top product consisting substantially of the lowest members of the components having an intermediate solubility in the solvent and a second bottom product, and separat'ely withdrawing the two top and two bottom products from the process. l

24. A process for separatinga normally liquid hydrocarbon fraction of a wide boiling temperature range obtained by distilling a petroleum ,oil and containing paraflinic and non-parainic hydrocarbons, comprising the steps of distilling said mixture in thepresence of a preferential solvent for non-parafnic hydrocarbons under conditions to produce a rst top product containing said solvent and a concentrate of the lowest boiling parsaid iirst top productand a second bottom product, and distilling the second bottom product in the presence of a preferential solvent for nonparaillnic hydrocarbons under conditions to pro- ,duce a. third top product containing a concentrate of paraihnic hydrocarbons and a third bottom product containing non-parainic hydrocarbons.

vent from the ilrst top product, distilling the first g top product substantially in the absence of a preferential solvent to produce a second bottom product containing a concentrate of the highest boiling paraillnic hydrocarbons contained in said iirst top product, and a second top product,\and distilling the second top product in the presence A of a preferential solvent for non-parafiinic hydrocarbons under conditions to produce a third top product containing a concentrate of paraiinic hydrocarbons and a third bottom product containing non-paraiiinic hydrocarbons.

PETRUS JURJEN ROELFSEMA. 

